The present invention relates to polymers, mixtures thereof suitable for use as suds volume and suds duration enhancers in detergent compositions useful for hand washing of dishware and cookware. The present invention also relates to polymers having sufficient cationic charge at a pH of from about 4 to about 12 to be effective as suds volume and suds duration enhancers.
Liquid detergent compositions which are suitable for hand dishwashing must satisfy several criteria in order to be effective. These compositions must be effective in cutting grease and greasy food material and once removed, must keep the greasy material from re-depositing on the dishware.
The presence of suds in a hand dishwashing operation has long been used as a signal that the detergent continues to be effective. However, depending upon the circumstances, the presence of suds or the lack thereof, has no bearing upon the efficacy of liquid detergents. Therefore, the consumer has come to rely upon a somewhat erroneous signal, the lack or absence of soap suds, to indicate the need for additional detergent. In many instances the consumer is adding an additional amount of detergent far in excess of the amount necessary to thoroughly clean the dishes. This wasteful use of detergent is especially true in hand dishwashing since the soiled cooking articles are usually cleaned in a xe2x80x9cwashing difficultyxe2x80x9d queue, for example, glasses and cups, which usually do not contact greasy food, are washed first, followed by plates and flatware, and finally pots and pans which contain the most residual food material and are usually, therefore, the xe2x80x9cgreasiestxe2x80x9d.
The lack of suds in the dishwater when pots and pans are usually cleaned, together with the visual inspection of the amount of residual food material on the cookware surface, typically compels the consumer to add additional detergent when a sufficient amount still remains in solution to effectively remove the soil and grease from the dishware or cookware surface. However, effective grease cutting materials do not necessarily produce a substantial amount of corresponding suds.
Accordingly, there remains a need in the art for liquid dishwashing detergents useful for hand washing dishware which have an enduring suds level while maintaining effective grease cutting properties. The need exists for a composition which can maintain a high level of suds as long as the dishwashing composition is effective. Indeed, there is a long felt need to provide a hand dishwashing composition which can be used efficiently by the consumer such that the consumer uses only the necessary amount of detergent to fully accomplish the cleaning task.
The present invention meets the aforementioned needs in that it has been surprisingly discovered that certain polymers serve as suds duration and suds volume extenders. The effective polymers of the present invention provide both increased suds volume and suds duration when formulated in a liquid detergent having a pH range of from about 4 to about 12 when measured as a 10% aqueous solution.
A first aspect of the present invention relates to detergent compositions suitable for use in hand dishwashing, said composition comprising:
a) an effective amount of a polymeric suds stabilizer comprising at least one monomeric unit of the formula: 
xe2x80x83wherein each of R1, R2 and R3 are indently selected from the group consisting of hydrogen, C1 to C6 alkyl, and mixtures thereof; L is selected from the group consisting of a bond, O, NR6, SR7R8 and mixtures thereof, wherein R6 is selected from the group consisting of hydrogen, C1 to C8 alkyl and mixtures thereof; each of R7 and R8 are independently hydrogen, O, C1 to C8 alkyl and mixtures thereof, or SR7R8 form a heterocyclic ring containing from 4 to 7 carbon atoms, optionally containing additional hetero atoms and optionally substituted; Z is selected from the group consisting of: xe2x80x94(CH2)xe2x80x94, (CH2xe2x80x94CHxe2x95x90CH)xe2x80x94, xe2x80x94(CH2xe2x80x94CHOH)xe2x80x94, (CH2xe2x80x94CHNR6)xe2x80x94, xe2x80x94(CH2xe2x80x94CHR14xe2x80x94O)xe2x80x94 and mixtures thereof; wherein R14 is selected from the group consisting of hydrogen, C1 to C6 alkyl and mixtures thereof; z is an integer selected from about 0 to about 12; A is NR4R5, wherein each of R4 and R5 are independently selected from the group consisting of hydrogen, C1-C8 linear or branched alkyl, alkyleneoxy having the formula:
xe2x80x94(R10O)yR11
xe2x80x83wherein R10 is C2-C4 linear or branched alkylene, and mixtures thereof; R11 is hydrogen, C1-C4 alkyl, and mixtures thereof; y is from 1 to about 10;, or NR4R5 form an heterocyclic ring containing from 4 to 7 carbon atoms, optionally containing additional hetero atoms, optionally fused to a benzene ring, and optionally substituted by C1 to C8 hydrocarbyl; and wherein said polymeric suds stabilizer has a molecular weight of from about 1,000 to about 2,000,000 daltons;
b) an effective amount of a detersive surfactant; and
c) the balance carriers and other adjunct ingredients;
provided the pH of a 10% aqueous solution of said composition is from about 4 to about 12.
The present invention also relates to methods for providing increased suds and increased duration of suds while hand washing dishware comprising the step of dissolving a composition according to the present invention in water to form a hand dish-washing solution and then washing dishware by hand in said solution. These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims.
All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (xc2x0C.) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.
The present invention relates to polymers which provide increased suds volume and increase suds duration during hand washing of dishware. The present invention also relates to liquid detergent compositions comprising polymers which provide extended suds volume and suds duration without sacrificing the grease cutting ability of said liquid detergent compositions.
In addition, the polymers of the present invention act together with surfactants and other adjunct ingredients, especially diamines, to provide for efficient grease cutting and anti-redepositon of grease.
Polymeric Suds Stabilizers
The polymeric suds stabilizers of the present invention are polymers comprising at least one monomeric unit of the formula: 
wherein each of R1, R2 and R3 are independently selected from the group consisting of hydrogen, C1 to C6 alkyl, and mixtures thereof, preferably hydrogen, C1 to C3 alkyl, more preferably, hydrogen or methyl. L is selected from the group consisting of a bond, O, NR6, SR7R8 and mixtures thereof, preferably, O, NR 6, wherein R6 is selected from the group consisting of hydrogen, C1 to C8 alkyl and mixtures thereof, preferably, hydrogen, C1 to C3, and mixtures thereof, more preferably hydrogen, methyl; each of R7 and R8 are independently hydrogen, O, C1 to C8 alkyl and mixtures thereof, preferably, hydrogen, C1 to C3, and mixtures thereof, more preferably hydrogen or methyl. By xe2x80x9cOxe2x80x9d, an oxygen linked via a double bond is meant, such as a carbonyl group. Furthermore this means that when either or both R7R8 is xe2x80x9cOxe2x80x9d, SR7R8 can have the following structures: 
Alternatively, SR7R8 form a heterocyclic ring containing from 4 to 7 carbon atoms, optionally containing additional hetero atoms and optionally substituted. For example SR7R8 can be: 
However, it is preferred that SR7R8, when present, is not a heterocycle.
When L is a bond it means that there is a direct link, or a bond, between the carbonyl carbon atom to Z, when z is not zero. For example: 
When L is a bond and z is zero, it means L is a bond from the carbonyl atom to A. For example: 
Z is selected from the group consisting of: xe2x80x94(CH2)xe2x80x94, (CH2xe2x80x94CHxe2x95x90CH)xe2x80x94, xe2x80x94(CH2xe2x80x94CHOH)xe2x80x94, (CH2xe2x80x94CHNR6)xe2x80x94, xe2x80x94(CH2xe2x80x94CHR14xe2x80x94O)xe2x80x94 and mixtures thereof, preferably xe2x80x94(CH2)xe2x80x94. R14 is selected from the group consisting of hydrogen, C1 to C6 alkyl and mixtures thereof, preferably hydrogen, methyl, ethyl and mixtures thereof; z is an integer selected from about 0 to about 12, preferably about 2 to about 10, more preferably about 2 to about 6.
A is NR4R5. Wherein each of R4 and R5 are is independently selected from the group consisting of hydrogen, C1-C8 linear or branched alkyl, alkyleneoxy having the formula:
xe2x80x94(R10O)yR11
wherein R10 is C2-C4 linear or branched alkylene, and mixtures thereof; R11 is hydrogen, C1-C4 alkyl, and mixtures thereof; y is from 1 to about 10. Preferably R4 and R5 are independently, hydrogen, C1 to C4 alkyl. Alternatively, NR4R5 can form a heterocyclic ring containing from 4 to 7 carbon atoms, optionally containing additional hetero atoms, optionally fused to a benzene ring, and optionally substituted by C1 to C8 hydrocarbyl. Examples of suitable heterocycles, both substituted and unsubstituted, are indolyl, isoindolinyl imidazolyl, imidazolinyl, piperidinyl pyrazolyl, pyrazolinyl, pyridinyl, piperazinyl, pyrrolidinyl, pyrrolidinyl, guanidino, amidino, quinidinyl, thiazolinyl, morpholine and mixtures thereof, with morpholino and piperazinyl being preferred. Furthermore the polymeric suds stabilizer has a molecular weight of from about 1,000 to about 2,000,000 preferably from about 5,000 to about 1,000,000, more preferably from about 10,000 to about 750,000, more preferably from about 20,000 to about 500,000, even more preferably from about 35,000 to about 300,000 daltons. The molecular weight of the polymeric suds boosters, can be determined via conventional gel permeation chromatography.
The polymeric suds stabilizers are polymers containing at least one monomeric unit of the formula: 
While, it is preferred that the polymeric suds stabilizers be selected from homopolymer, copolymers and terpolymers, other polymers (or multimers) of the at least one monomeric unit, the polymeric suds stabilizers can also be envisioned via polymerization of the at least one monomeric unit with a wider selection of monomers. That is, all the polymeric suds stabilizers can be a homopolymers, copolymers, terpolymers, etc. of the at least one monomeric unit, or the polymeric suds stabilizer can be copolymers, terpolymers, etc. containing one, two or more of the at least one monomeric unit and one, two or more monomeric units other than the at least one monomeric unit. For example a suitable homopolymer is: 
wherein R1, R4, R5 and z are as hereinbefore defined. For example a suitable copolymer is: 
wherein R1, R4, R5 and z are as hereinbefore defined; and 
wherein R1 and L are as hereinbefore defined, and B is selected from the group consisting of hydrogen, C1 to C8 hydrocarbyl, NR4R5, and mixtures thereof; wherein each of R4 and R5 are independently selected from the group consisting of hydrogen, C1 to C8 alkyl, and mixtures thereof, or NR4R5 form a heterocyclic ring containing from 4 to 7 carbon atoms, optionally containing additional hetero atoms, optionally fused to a benzene ring, and optionally substituted by C1 to C8 hydrocarbyl;
wherein ratio of (i) to (ii) is from about 99:1 to about 1:10.
Some preferred examples of 
are: 
For example a copolymer can be made from two monomers, G and H, such that G and H are randomly distributed in the copolymer, such as
GHGGHGGGGGHHG . . . etc.
or G and H can be in repeating distributions in the copolymer, for example
GHGHGHGHGHGHGH . . . etc.,
or
GGGGGHHGGGGGHH . . . etc.,
The same is true of the terpolymer, the distribution of the three monomers can be either random or repeating.
For example a suitable polymeric suds stabilizer, which is a copolymer is: 
wherein R1, R4, R5 and z are as hereinbefore defined; and 
wherein R1 Z and z are as hereinbefore defined, each of R12 and R13 are independently selected from the group consisting of hydrogen, C1 to C8 alkyl and mixtures thereof, preferably, hydrogen, C1 to C3, and mixtures thereof, more preferably hydrogen, methyl, or R12 and R13 form a heterocyclic ring containing from 4 to 7 carbon atoms; and R15 is selected from the group consisting of hydrogen, C1 to C8 alkyl and mixtures thereof, preferably, hydrogen, C1 to C3, and mixtures thereof, more preferably hydrogen, methyl,
wherein ratio of (i) to (ii) is from about 99:1 to about 1:10.
Some preferred at least one monomeric units, which can be additionally combined together to from copolymers and terpolymers include: 
An example of a preferred homopolymer is 2-dimethylaminoethyl methacrylate (DMAM) having the formula: 
Some preferred copolymers include:
copolymers of 
An example of a preferred copolymer is the (DMA)/(DMAM) copolymer having the general formula: 
wherein the ratio of (DMA) to (DMAM) is about 1 to about 10, preferably about 1 to about 5, more preferably about 1 to about 3.
An example of a preferred copolymer is the (DMAM)/(DMA) copolymer having the general formula: 
wherein the ratio of (DMAM) to (DMA) is about 1 to about 5, preferably about 1 to about 3.
The liquid detergent compositions according to the present invention comprise at least an effective amount of the polymeric suds stabilizers described herein, preferably from about 0.01% to about 10%, more preferably from about 0.05% to about 5%, most preferably from about 0.1% to about 2% by weight, of said composition. What is meant herein by xe2x80x9can effective amount polymeric suds stabilizersxe2x80x9d is that the suds volume and suds duration produced by the presently described compositions are sustained for an increased amount of time relative to a composition which does not comprise one or more of the polymeric suds stabilizer described herein. Additionally, the polymeric suds stabilizer can be present as the free base or as a salt. Typical counter ions include, citrate, maleate, sulfate, chloride, etc.
Anionic Surfactants
The anionic surfactants useful in the present invention are preferably selected from the group consisting of, linear alkylbenzene sulfonate, alpha olefin sulfonate, paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfate, alkyl sulfonates, alkyl alkoxy carboxylate, alkyl alkoxylated sulfates, sarcosinates, taurinates, and mixtures thereof. An effective amount, typically from about 0.5% to about 90%, preferably about 5% to about 60%, more preferably from about 10 to about 30%, by weight of anionic detersive surfactant can be used in the present invention.
Alkyl sulfate surfactants are another type of anionic surfactant of importance for use herein. In addition to providing excellent overall cleaning ability when used in combination with polyhydroxy fatty acid amides (see below), including good grease/oil cleaning over a wide range of temperatures, wash concentrations, and wash times, dissolution of alkyl sulfates can be obtained, as well as improved formulability in liquid detergent formulations are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali (Group IA) metal cation (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like. Typically, alkyl chains of C12-16 are preferred for lower wash temperatures (e.g., below about 50xc2x0 C.) and C16-18 alkyl chains are preferred for higher wash temperatures (e.g., above about 50xc2x0 C.).
Alkyl alkoxylated sulfate surfactants are another category of useful anionic surfactant. These surfactants are water soluble salts or acids typically of the formula RO(A)mSO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperidinium and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof. Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18 alkyl polyethoxylate (2.25) sulfate, C12-C18 alkyl polyethoxylate (3.0) sulfate, and C12-C18 alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassium. Surfactants for use herein can be made from natural or synthetic alcohol feedstocks. Chain lengths represent average hydrocarbon distributions, including branching.
Examples of suitable anionic surfactants are given in xe2x80x9cSurface Active Agents and Detergentsxe2x80x9d (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
Secondary Surfactants
Secondary detersive surfactant can be selected from the group consisting of nonionics, cationics, ampholytics, zwitterionics, and mixtures thereof. By selecting the type and amount of detersive surfactant, along with other adjunct ingredients disclosed herein, the present detergent compositions can be formulated to be used in the context of laundry cleaning or in other different cleaning applications, particularly including dishwashing. The particular surfactants used can therefore vary widely depending upon the particular end-use envisioned. Suitable secondary surfactants are described below. Examples of suitable nonionic, cationic amphoteric and zwitterionic surfactants are given in xe2x80x9cSurface Active Agents and Detergentsxe2x80x9d (Vol. I and II by Schwartz, Perry and Berch).
Nonionic Detergent Surfactants
Suitable nonionic detergent surfactants are generally disclosed in U.S. Pat. 3,929,678, Laughlin et al., issued Dec. 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non-limiting classes of useful nonionic surfactants include: amine oxides, alkyl ethoxylate, alkanoyl glucose amide, alkyl betaines, sulfobetaine and mixtures thereof.
Amine oxides are semi-polar nonionic surfactants and include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula 
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include C10-C18 alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides. Preferably the amine oxide is present in the composition in an effective amount, more preferably from about 0.1% to about 20%, even more preferably about 0.1% to about 15%, even more preferably still from about 0.5% to about 10%,by weight.
The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. In general, the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include Igepal(copyright) CO-630, marketed by the GAF Corporation; and Triton(copyright) X-45, X-114, X-100, and X-102, all marketed by the Rohm and Haas Company. These compounds are commonly referred to as alkyl phenol alkoxylates, (e.g., alkyl phenol ethoxylates).
The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol(copyright) 15-S-9 (the condensation product of C11-C15 linear secondary alcohol with 9 moles ethylene oxide), Tergitol(copyright) 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol(copyright) 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), Neodol(copyright) 23-6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), Neodol(copyright) 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodol(copyright) 45-4 (the condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and Kyro(copyright) EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter and Gamble Company. Other commercially available nonionic surfactants include Dobanol 91-8(copyright) marketed by Shell Chemical Co. and Genapol UD-080(copyright) marketed by Hoechst. This category of nonionic surfactant is referred to generally as xe2x80x9calkyl ethoxylates.xe2x80x9d
The preferred alkylpolyglycosides have the formula
R2O(CnH2nO)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
Fatty acid amide surfactants having the formula: 
wherein R6 is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and xe2x80x94(C2H4O)xH where x varies from about 1 to about 3.
Preferred amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
Preferably the nonionic surfactant, when present in the composition, is present in an effective amount, more preferably from about 0.1% to about 20%, even more preferably about 0.1% to about 15%, even more preferably still from about 0.5% to about 10%,by weight.
Polyhydroxy Fatty Acid Amide Surfactant
The detergent compositions hereof may also contain an effective amount of polyhydroxy fatty acid amide surfactant. By xe2x80x9ceffective amountxe2x80x9d is meant that the formulator of the composition can select an amount of polyhydroxy fatty acid amide to be incorporated into the compositions that will improve the cleaning performance of the detergent composition. In general, for conventional levels, the incorporation of about 1%, by weight, polyhydroxy fatty acid amide will enhance cleaning performance.
The detergent compositions herein will typically comprise about 1% weight basis, polyhydroxy fatty acid amide surfactant, preferably from about 3% to about 30%, of the polyhydroxy fatty acid amide. The polyhydroxy fatty acid amide surfactant component comprises compounds of the structural formula: 
wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C15 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of xe2x80x94CH2xe2x80x94(CHOH)nxe2x80x94CH2OH, xe2x80x94CH(CH2OH)xe2x80x94(CHOH)n-1xe2x80x94CH2OH, xe2x80x94CH2xe2x80x94(CHOH)2(CHORxe2x80x2)(CHOH)xe2x80x94CH2OH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and Rxe2x80x2 is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly xe2x80x94CH2xe2x80x94(CHOH)4xe2x80x94CH2OH.
Rxe2x80x2 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
R2xe2x80x94COxe2x80x94N less than  can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amination step to form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published Feb. 18, 1959, by Thomas Hedley and Co., Ltd., U.S. Pat. No. 2,965,576, issued Dec. 20, 1960 to E. R. Wilson, and U.S. Pat. No. 2,703,798, Anthony M. Schwartz, issued Mar. 8, 1955, and U.S. Pat. No. 1,985,424, issued Dec. 25, 1934 to Piggott, each of which is incorporated herein by reference.
Diamines
The preferred liquid detergent compositions of the present invention further comprise one or more diamines, preferably an amount of diamine such that the ratio of anionic surfactant present to the diamine is from about 40:1 to about 2:1. Said diamines provide for increased removal of grease and greasy food material while maintaining suitable levels of suds.
It is preferred to include from about 0.1% to about 15%, preferably from about 0.5% to about 10%, more preferably from about 0.5% to about 6% even more preferably still from about 0.5% to about 1.5%, by weight, of a diamines in the preferred liquid detergent compositions.
The diamines suitable for use in the compositions of the present invention have the formula: 
wherein each R9 is independently selected from group consisting of hydrogen, C1-C4 linear or branched alkyl, alkyleneoxy having the formula:
xe2x80x94(R10O)yR11
wherein R10 is C2-C4 linear or branched alkylene, and mixtures thereof; R11 is hydrogen, C1-C4 alkyl, and mixtures thereof; y is from 1 to about 10; X is a unit selected from:
i) C3-C10 linear alkylene, C3-C10 branched alkylene, C3-C10 cyclic alkylene, C3-C10 branched cyclic alkylene, an alkyleneoxyalkylene having the formula:
xe2x80x94(R10O)yR10xe2x80x94
wherein R10 and y are the same as defined herein above;
ii) C3-C10 linear, C3-C10 branched linear, C3-C10 cyclic, C3-C10 branched cyclic alkylene, C6-C10 arylene, wherein said unit comprises one or more electron donating or electron withdrawing moieties which provide said diamine with a pKa greater than about 8; and
iii) mixtures of (i) and (ii)
The preferred diamines of the present invention have a pK1 and pK2 which are each in the range of from about 8 to about 11.5, preferably in the range of from about 8.4 to about 11, more preferably from about 8.6 to about 10.75. For the purposes of the present invention the term xe2x80x9cpKaxe2x80x9d stands equally well for the terms xe2x80x9cpK1xe2x80x9d and xe2x80x9cpK2xe2x80x9d either separately or collectively. The term pKa as used herein throughout the present specification in the same manner as used by those of ordinary skill in the art. pKa values are readily obtained from standard literature sources, for example, xe2x80x9cCritical Stability Constants: Volume 2, Aminesxe2x80x9d by Smith and Martel, Plenum Press, New York and London, (1975).
As an applied definition herein, the pKa values of the diamines are specified as being measured in an aqueous solution at 25xc2x0 C. having an ionic strength of from about 0.1 to about 0.5 M. As used herein, the pKa is an equilibrium constant dependent upon temperature and ionic strength, therefore, value reported by literature references, not measured in the above described manner, may not be within full agreement with the values and ranges which comprise the present invention. To eliminate ambiguity, the relevant conditions and/or references used for pKa""s of this invention are as defined herein or in xe2x80x9cCritical Stability Constants: Volume 2, Aminesxe2x80x9d. One typical method of measurement is the potentiometric titration of the acid with sodium hydroxide and determination of the pKa by suitable methods as described and referenced in xe2x80x9cThe Chemist""s Ready Reference Handbookxe2x80x9d by Shugar and Dean, McGraw Hill, N.Y., 1990.
Preferred diamines for performance and supply considerations are 1,3-bis(methylamino)cyclohexane, 1,3-diaminopropane (pK1=10.5; pK2=8.8), 1,6-diaminohexane (pK1=11; pK2=10), 1,3-diaminopentane (Dytek EP) (pK1=10.5; pK2=8.9), 2-methyl 1,5-diaminopentane (Dytek A) (pK1=11.2; pK2=10.0). Other preferred materials are the primary/primary diamines having alkylene spacers ranging from C4-C8. In general, primary diamines are preferred over secondary and tertiary diamines.